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Progress in Chemistry 2018, No.12 Previous issue Next issue

In this issue:

Review
Crystal Structure and Electronic Structure of Uranium Nitrides
Xiaofang Wang, Yin Hu, Qifa Pan, Ruilong Yang, Zhong Long, Kezhao Liu
2018, 30 (12): 1803-1818 | DOI: 10.7536/PC180303
Published: 15 December 2018
Abstract
Uranium nitrides have aroused more and more attention due to their unique physical and chemical properties and their excellent performance in applications such as nuclear fuel and anti-corrosion coating for uranium metal. In U-N system, five structures of uranium nitrides, including NaCl-type UN, HgIn-type UN, Mn2O3-type α-U2N3, La2O3-type β-U2N3 and CaF2-type UN2, have been identified and studied extensively. Up to now, because of the complex nonstoichiometric problems of uranium nitrides, the understanding of the transformation relationship between these phases is still ambiguous. In addition, the basic physical properties of uranium nitrides have been fundamentally changed due to the difference in electronic structures of uranium nitrides with different nitrogen content. The studies of the crystal structure and electronic structure of uranium nitrides are the first step in exploring the causes of their excellent performances, and have attracted much attention in recent years. Based on the analysis and summary of the literatures, as well as the research results of our group, this paper reviews the main progress in the study of the crystal structure and electronic structure of uranium nitrides. The phase transformation and electronic structure evolutions of uranium nitrides are summarized, which is expected to provide reference for the experimental studies and functional applications of uranium nitrides.
Contents
1 Introduction
2 Composition and crystal structure of uranium nitrides
2.1 Crystal structure of UN
2.2 Crystal structure of U2N3
2.3 Crystal structure of UN2
3 Phase relation of uranium nitrides
3.1 Phase relation between NaCl type UN and R3m type UN
3.2 Phase relation between NaCl type UN and U2N3
3.3 Phase relation between α-U2N3 and β-U2N3
3.4 Phase relation between UN2 and α-U2N3
3.5 Phase transition mechanism of uranium nitrides
4 Electronic structures of uranium nitrides
4.1 Electronic structure of UN
4.2 Electronic structure of nitrogen-rich nitrides
5 Conclusion and outlook
Organic Radical Reactions in Water Medium
Yiling Huang, Wenting Wei*
2018, 30 (12): 1819-1826 | DOI: 10.7536/PC180225
Published: 15 December 2018
Abstract
The greenization of chemical reaction solvent is an inevitable trend of green chemistry in the future. And it is the goal of chemists to replace the traditional organic solvents with water which is abundant, cheap, non-toxic and pollution-free. Radical reaction has gradually become an important strategy for organic synthesis due to its high activity and mild reaction conditions. This review summarizes the advancements of organic radical reaction in water medium in recent five years on the basis of different chemical bonds.
Contents
1 Introduction
2 The construction of C-C bonds
3 The construction of C-N bonds
4 The construction of C-O bonds
5 The construction of C-S bonds
6 Conclusion
Synthesis of Homoharringtonine and Harringtonine
Yu Dong, Haibo Li, Jin Li, Lei Feng, Zhiwei Zhang*
2018, 30 (12): 1827-1835 | DOI: 10.7536/PC180227
Published: 15 December 2018
Abstract
Natural drugs homoharringtonine and harringtonine are minor alkaloids isolated from the leaves and stems of plum yew Cephalotaxus harringtonia, an evergreen tree native of the southern provinces of China. Structurally, two natural drugs are all chiral compounds and have a common skeleton cephalotaxine, and the ester side chains bear chiral tertiary alcohol at α position. Because of the formidable steric bulk of both the keleton cephalotaxine and ester side chain, the esterification of both sections is extremely challenging. A less hindered side chain intermediate is key element to success for this coupling reaction. Consequently, chemists continuously designed and synthesized structurally diverse side chain intermediates such as α-ketoacids, four-membered lactone heterocycles, tetrahydrofuran heterocycles, tetrahydropyran heterocycles, and seven-membered lactone heterocycles, enabling the completion of synthesis of homoharringtonine, harringtonine and other related natural products. Based on our studies toward the synthesis of Cephalotaxus alkaloids, this paper reviews the strategic development towards the synthesis of Cephalotaxus natural drugs and other products by the types of side chain intermediates, including not only recent strategy advances but also synthetic methods developed by respected older generation chemists.
Contents
1 Introduction
2 Synthesis of homoharringtonine
2.1 α-Ketoacids as coupling partners
2.2 Tetrahydropyran intermediate as coupling partner
2.3 Four-membered lactone intermediate as coupling partner
3 Synthesis of harringtonine
3.1 α-Ketoacid as coupling partner
3.2 Dihydrofuran intermediate as coupling partner
3.3 Seven-membered lactone intermediate as coupling partner
4 Synthesis of anhydroharringtonine
4.1 α-Ketoacid as coupling partner
4.2 Tetrahydrofuran intermediate as coupling partner
5 Synthesis of homodeoxyharringtone
5.1 α-Ketoacid as coupling partner
5.2 Four-membered lactone intermediate as coupling partner
6 Synthesis of deoxyharringtone
6.1 α-Ketoacids as coupling partners
6.2 Four-membered lactone intermediate as coupling partner
7 Synthesis of isoharringtonine, nordeoxyharringtonine and homoneoharringtonine
8 Conclusion
Synthesis of Biobased Furan-Containing Polyamides
Weijun Huang, Ning Zhu*, Zheng Fang, Kai Guo*
2018, 30 (12): 1836-1843 | DOI: 10.7536/PC180338
Published: 15 December 2018
Abstract
As the increasing concerns about the environmental protection and fossil resource issues, it is important to develop biobased polymer materials from renewable biomass resources. As one of the most valuable biogenic platform compounds, furandicarboxylic acid and derivatives, have attracted much attention in synthesis of fine chemicals and biobased materials. In recent years, varied biobased polyamide homo-and copolymers have been successfully prepared via polycondensations between furandicarboxylic acid and derivative and diamines, including melt polymerization, solution polymerization, interfacial polycondensation, and solid phase polycondensation. Herein, recent progress in synthesis of renewable furan-containing polyamides are detail introduced. Polyamides with different structures present favorable thermal properties and mechanical performance. In the meantime, varied measures have been taken to improve the molecular weight, yield, catalytic efficiency, structural diversity, etc. Moreover, the challenges and modifications of biobased furan-containing polyamides for further industrial applications are discussed and prospected.
Contents
1 Introduction
2 Synthesis of biobased furan-containing polyamides
2.1 Synthesis of furan-aromatic polyamide
2.2 Synthesis of furan-aliphatic polyamide
2.3 Study on thermodynamic properties of biobased furan-containing polyamide
3 Synthesis of biobased furan-containing polyamide copolymers
3.1 Synthesis of furan-aromatic copolyamide
3.2 Synthesis of furan-aliphatic copolyamide
4 Conclusion and outlook
Solid-State Nuclear Magnetic Resonance Techniques for Polymer Quantitative Investigation
Jie Shu, Jiali Gu, Huipeng Zhao
2018, 30 (12): 1844-1851 | DOI: 10.7536/PC180308
Published: 15 December 2018
Abstract
Polymers have been widely used nowadays owing to their versatile properties, which firmly relate to their molecular physical and chemical structures. Therefore, the quantitative and quasi-quantitative characterization of polymer chemical and physical structures is essential in developing novel polymer materials. Among various characterization methods, solid-state nuclear magnetic resonance (SSNMR) plays an essential role in quantitative investigation, which is capable of providing quantitative information on chemical structure of polymers, phase composition of multi-phase systems as well as component content of block copolymers or polymer blends. However, traditional SSNMR quantitative method consumes very long experimental time for most of the systems. Cross polarization (CP) method, as a widely-used SSNMR technique, is capable of providing a spectrum within much shorter time. However, CP is mostly not quantitative. Therefore, several quantitative CP methods were proposed in past years, which are both quantitative and time-saving. In this article, we present an overview of the SSNMR quantitative methods, including the traditional techniques and the newly proposed CP methods in past twelve years. Basic principle and properties of each method are elucidated. In addition, several application examples are introduced which is aimed to assist the researchers in their works of polymer quantitative study.
Contents
1 Introduction
2 SSNMR quantitative techniques and the applications for polymer study
2.1 Direct polarization techniques (DP and DD)
2.2 Cross polarization technique (CP)
2.3 Quantitative CP methods
3 Conclusion
Silicone Self-Healing Materials
Long Cheng, Dajiang Yu, Jiajian You, Teng Long, Susu Chen, Chuanjian Zhou
2018, 30 (12): 1852-1862 | DOI: 10.7536/PC180312
Published: 15 December 2018
Abstract
Silicone self-healing materials are widely used in wearable equipment, smart coatings and other fields. In this review, we detail the self-healing properties, mechanism and latest research progress for both extrinsic and intrinsic silicone self-healing materials. In the section of extrinsic silicone self-healing materials, a variety of silicone-specific reactions, including light-induced radical reaction, condensation curing and hydrosilylation, that have been exploited to achieve self-healing properties are discussed. Similarly, mechanisms to achieve intrinsic self-healing through reversible chemical reactions, metal-ligand coordination, supramolecular interaction and other methods are described in the following section, as well as their properties. To be more specific, reversible chemical reactions could be divided into Diels-Alder reaction, acylhydrazone bonds, ester bonds and Schiff-base bonds, while supramolecular interactions consist of hydrogen bonding and π-π stacking. Besides, some other self-healing systems such as minimizing surface free energy, thiol-silver nanoparticles interaction and reconstruction reaction are introduced. Based on the review, a brief appraisal of the challenges and orientation for future developments in this field is presented.
Contents
1 Introduction
2 Extrinsic silicone self-healing materials
2.1 Light-induced
2.2 Condensation-curing
2.3 Hydrosilylation
3 Intrinsic silicone self-healing materials
3.1 Reversible chemical reaction
3.2 Metal-ligand coordination
3.3 Supramolecular interaction
3.4 Others
4 Conclusion
Bioinspired Micro-Nano Fibrous Adhesion Materials
Chen Zhou, Juntao Wu*
2018, 30 (12): 1863-1873 | DOI: 10.7536/PC180425
Published: 15 December 2018
Abstract
Biological materials that are unified in function and structure in the natural world are the inspirations source of innovation for human society. Among the numerous biological materials with excellent performance,biological micro-nano fibers with unique adhesion properties have always been one of the hotspots in the fields of bionics research. The adhesion of biological micro-nano fibers is a peculiar phenomenon in nature. Numerous biological fibrous materials with special adhesion properties and functions play an important role in biological movement, defense, prey capture and other aspects. The adhesion of biological micro-nano fibers mainly includes adhesion on fiber tip, like gecko foot seta tip, and adhesion on fiber surface, like spider silk surface. It is found that such adhesion mainly comes from the special micro-nano structures and surface properties of micro-nano fibers. Inspired by the adhesive biological fibers, many excellent artificial micro-nano fibrous adhesion materials have been designed and developed. Micro-nano fibrous adhesion materials have a wide variety of practical applications in dry adhesive, high efficiency water capturing, air filtration and other fields. In this paper, the recent researches on adhesion mechanism of biological micro-nano fibers and the corresponding bioinspired materials are introduced, with a focus on gecko foot seta and spider silk. Meanwhile, the future development trend of this field is also proposed.
Contents
1 Introduction
2 Adhesion on tip of micro-nano fibers
2.1 Micro-nano fibrillar structures of animals adhesion toes
2.2 The hierarchical micro-nano fibrous structures and adhesion mechanisms of gecko foot
2.3 Bioinspired micro-nano fibrous array adhesion materials
3 Adhesion on surface of micro-nano fibers
3.1 Adhesion phenomena and mechanisms on surface of spider silk
3.2 Fabrications and applications of micro-nano fibrous adhesion materials inspired by spider silk
4 Conclusion
Smart Responsive Superwetting Materials
Mengnan Qu*, Mingjuan Yuan, Jiao He, Menghui Xue, Jinmei He*
2018, 30 (12): 1874-1886 | DOI: 10.7536/PC180315
Published: 15 December 2018
Abstract
In recent years, superwetting materials have received increasing attention because of their novelty and excellent performances, including self-cleaning, anti-fouling, anti-corrosion and oil-water separation, and played an important role in the real life and industry production field. However, with the continuous progress of preparation technology and the gradual deepening of research and exploration, the existing single superwetting materials can no longer meet the needs of real life, such as increasing oil spills, controlled release of drugs and microfluidic devices. On this basis, the superwetting materials that are able to respond to external stimuli, that is, the smart responsive superwetting materials come into being. In this review, basic theories and influence factors of solid surface wettability are introduced firstly. Secondly, according to the difference of external stimuli, the research and progress of the smart responsive superwetting materials, including thermoresponsive, photo-responsive, pH-responsive and electricity-responsive are reviewed. Furthermore, the wettability conversion mechanisms and properties of these smart responsive superwetting materials mentioned in the review are introduced. In order to reveal the importance of roughness to the realization of superwetting conversion, we explain it in micro-and nano-scale. Finally, some existing problems are discussed and the future research directions in this field are proposed.
Contents
1 Introduction
2 Wettability of solid surface
3 Single stimuli-responsive materials
3.1 Thermoresponsive materials
3.2 Photo-responsive materials
3.3 pH-responsive materials
3.4 Electricity-responsive materials
3.5 Solvent-responsive materials
3.6 Other responsive materials
4 Dual-and multiresponsive switchable materials
5 Existing problems
6 Conclusion
Application of Low Surface Energy Compounds to the Superwetting Materials
Lingang Hou, Lili Ma, Yichen Zhou, Yu Zhao, Yi Zhang, Jinmei He*
2018, 30 (12): 1887-1898 | DOI: 10.7536/PC180345
Published: 15 December 2018
Abstract
Recently, the superwetting materials have become a new research hotspot due to their potential application in self-cleaning, microfluidics transmission, biocompatibility etc. In addition to the creating of rough micro-nanoscale structure, the control of surface energy of the materials is also a vital factor for fabricating the superwetting materials. With the deepening of research on the mechanism of the wettability of superwetting surface, more and more kinds of low surface energy compounds with different structures have been used to decrease the surface energy. Based on the molecular structures and compound types, this paper reviews the low surface energy compounds in fabricating the superwetting materials, concludes the effects of pH value, temperature, concentration and solvent on the low surface energy materials, and summarizes the selection and application of low surface energy compounds for improving the mechanical strength, and preparing materials of wettability transformation and different wettability modification. Finally, some existing problems are discussed and the future research directions in this field are proposed.
Contents
1 Introduction
2 Types of the low surface energy compounds
2.1 Silane coupling agent
2.2 Aluminate coupling agent
2.3 Saturated fatty compounds
2.4 Low surface energy polymers with 3D structure
2.5 Composite compounds with low surface energy
3 Factors affecting the low surface energy of materials
3.1 pH
3.2 Temperature
3.3 Concentration
3.4 Solvent
3.5 Other factors
4 Selection and application of low surface energy compounds
4.1 Mechanical strength
4.2 Wettability transformation
4.3 Different wettability
5 Existing problems
6 Conclusion and outlook
Preparation of Hollow Mesoporous Materials by Polymer-Based Templates
Zhichao Yu, Chun Tang, Li Yao, Qing Gao, Zushun Xu, Tingting Yang
2018, 30 (12): 1899-1907 | DOI: 10.7536/PC180409
Published: 15 December 2018
Abstract
Hollow mesoporous materials (HMMs), especially the silica-based and carbon-based HMMs, are of great importance on account of their tunable pore sizes and structures, chemical stability, facile surface functionalization, high guest molecules uploading and broad applications in the field of catalysis, biology and energy storage. Template method is one of the most effective methods to prepare HMMs. Controlling HMMs can be realized by modulating the templates. Polymer-based templates, including micelles, self-assemblies of block polymers, polymer latex particles, natural/synthetic macromolecules and sophisticate-structured macromolecules (dentrimer and brushes), are successfully applied in preparing HMMs in desired forms. Recent progress in the synthesis of hollow mesoporous materials with different polymer-based templates are reviewed. Compared with the conventional surfactant/inorganic oxide templates, polymer-based templates are easy to undergo surface modification and possess ampler self-assembly morphologies such as spheres, vesicles and rods under more gentle and controllable synthetic conditions. Especially the unique hollow cavity of HMMs is more efficient to capture the noble metal nanoparticles as cores. Applications of noble-metal-uploading hollow mesoporous materials as catalytic carriers are discussed mainly in three aspects including chemical catalysis, electrocatalysis and photoelectric catalysis. At the same time, the problems hindering the development of HMMs are pointed out, and the application prospect of HMMs in catalysis is prospected.
Contents
1 Introduction
2 Polymer-based templates
2.1 Self-assemblies of block copolymers
2.2 Emulsion droplet and polymer latex particles
2.3 Natural/synthetic biological macromolecules
2.4 Sophisticate-structured polymers
3 Hollow mesoporous materials as catalytic carriers
4 Conclusion
The Application of Nanoparticles in Drug Delivery
Dongdong Zhang, Jingmin Liu, Yaoyao Liu, Meng Dang, Guozhen Fang, Shuo Wang
2018, 30 (12): 1908-1919 | DOI: 10.7536/PC180217
Published: 15 December 2018
Abstract
At present, application of nanoparticles for drug delivery and tumor targeting has become a very popular concept to improve the diagnosis and treatment level of tumor tissues. People have long expected to use nanotechnology, which is easy to manufacture, cost effective, low toxic, to improve the efficiency of treatment. However, the transfer efficiency is extremely low according to the reported literature, only about 0.7% of the administered nanoparticles reach tumor. In this paper, we analyze the influence factor of low efficiency on nanoparticle targeted delivery, including transport pathway of nanoparticles, the barrier in the course of nanoparticles transport, and in vivo clearance of nanoparticles. For the applications of nanoparticles, firstly, we introduce the preparation methods of polymer nanoparticles and the current application in clinic; followed by the introduction of iron oxide nanoparticles, which has great potential clinical application value, combined with drug by different binding modes; we also introduce the widely studied mesoporous silica nanoparticles and its several different drug delivery systems. The biomimetic nanoparticles of cell membrane is also recommended due to its great advantage in constructing drug delivery system. Finally, the future research of nanoparticles in drug delivery is prospected. We hope that we could promote the application of nanoparticles in drug delivery and accelerate the clinical translation of nanomedicine through systematic study on nanoparticles delivery.
Contents
1 Introduction
2 The delivery efficiency of nanoparticles and consequences
3 The barrier in the course of nanoparticles transport
4 The in vivo clearance of nanoparticles
4.1 Mononuclear phagocytic system identificaion
4.2 Macrophage uptake nanoparticles
4.3 Renal clearance
5 The toxicity of nanoparticles
6 The application of nanoparticles in drug delivery
6.1 Polymer nanoparticles
6.2 Magnetic iron oxide nanoparticles
6.3 Mesoporous silica nanoparticles
6.4 Biomimetic nanoparticles of cell membrane
7 Conclusion
Design and Fabrication of Magnetically Responsive Drug Delivery Carriers
Hongmei Bi, Xiaojun Han
2018, 30 (12): 1920-1929 | DOI: 10.7536/PC180413
Published: 15 December 2018
Abstract
Development and application of hybrid magnetic biomaterials has been attracting great attention in biomedical applications. Magnetic nanoparticles (MNPs) have emerged as a promising theranostic tool for diagnostic imaging, drug delivery and novel therapeutics because of their functionalization, targeted delivery, controllable drug release and image-guided capabilities. Remotely triggered magnetic drug delivery systems based on MNPs or doped iron oxides can enhance the drug delivery efficiency to the cancerous regions with low toxicity or without toxicity to the surrounding healthy cells. In order to fabricate safer and more effective magnetic drug delivery systems, different materials or ligands such as biomolecules, polymers even natural extractive are combined with MNPs by this hybrid approach, which has created entirely new advanced compositions with truly unique properties for drug delivery. So far, the responsive nano-structured magnetic drug delivery carriers have been extensively explored for remotely controlled drug release although there are still some difficulties and challenges. In this review, we summarize the recent advances in the design and fabrication of hybrid magnetic drug delivery carriers as remotely controlled therapeutic systems with a focus on the materials for delivery carriers fabrication including phospholipid molecules, polymers, mesoporous micro-nanomaterials, natural extractive, etc. In addition, the advantages, limits and prospects of current hybrid targeted magnetic drug delivery carriers are also briefly summarized.
Contents
1 Introduction
2 Fabrication and application of magnetic response drug delivery carriers
2.1 Drug delivery carriers based on phospholipid and magnetic nanoparticles
2.2 Drug delivery carriers based on polymer and magnetic nanoparticles
2.3 Drug delivery carriers based on porous micro-nanomaterial and magnetic nanoparticles
2.4 Drug delivery carriers based on natural extractive and magnetic nanoparticles
3 Conclusion
The Control of Reduction Degree of Graphene Oxide
Liping Chen, Rong Yang, Yinglin Yan, Chaojiang Fan, Mangmang Shi, Yunhua Xu
2018, 30 (12): 1930-1941 | DOI: 10.7536/PC180408
Published: 15 December 2018
Abstract
Graphene, a two-dimensional material with monoatomic thickness, possesses a series of excellent properties, such as flexibility and electrical conductivity, which makes it widely applied in many fields. Oxidation-reduction method is the most commonly used and promising method for the preparation of graphene. However, large amounts of oxygen-containing functional groups, such as hydroxyl, epoxy, carboxyl and carbonyl groups, are formed on the planes and edges of the graphene during the oxidation process, which makes its conjugated structure destroyed, causing the excellent electrical conductivity decreased. Consequently, graphene oxide needs to be reduced by removing the oxygen-containing functional groups to recover conjugated structure. Interestingly, graphene-based materials need both a certain amount or types of oxygen-containing functional groups on graphene oxide which determines the characteristic of graphene oxide, chemical activity, hydrophilicity, band gap or defects, etc., and the characteristic of graphene, such as high electrical conductivity, for application in many fields. The control of reduction degree of graphene oxide, obtaining partially reduced graphene oxide, can not only make most use of the merits of oxygen-containing functional groups and ensure enough conductivity, but also obtain the partially reduced graphene oxide with determined types and amount of oxygen-containing functional groups on the requirements of the applications, realizing the diverse applications of graphene, such as adsorption, electroatalysis, photocatalysis, and sensor. The methods for controlling reduction degree of graphene oxide include chemical reduction method, thermal reduction (thermal annealing, hydrothermal and solvethermal reduction) and electrochemical reduction. Herein research progress on the controlling conditions of partially reduced graphene oxide, reduction mechanism and effect, comparison of those reduction methods as well as the applications of partially reduced graphene oxide are reviewed, and current challenges and research directions are also presented.
Contents
1 Introduction
2 Reduction degree of GO controlled by chemical reduction method
2.1 Types and concentration of reduction agent
2.2 Reduction temperature
2.3 Reaction medium and pH
2.4 Reduction time
3 Reduction degree of GO controlled by thermal reduction methods
3.1 Thermal annealing
3.2 Hydrothermal (solvothermal)
4 Reduction degree of GO controlled by electrochemical reduction method
4.1 Reduction potential
4.2 Reduction time
5 Reduction mechanism and effect
5.1 Reduction mechanism of chemical reduction
5.2 Reduction mechanism of thermal reduction
5.3 Reduction mechanism of electrochemical reduction
5.4 Comparison of different reduction methods
6 Applications of controlling reduction degree
7 Conclusion
Multifunctional Lithium-Sulfur Battery Separator
Kai Yang, Shengnan Zhang, Dongmei Han, Min Xiao, Shuanjin Wang*, Yuezhong Meng*
2018, 30 (12): 1942-1959 | DOI: 10.7536/PC180405
Published: 15 December 2018
Abstract
Lithium-sulfur batteries, with the advantages of rich sulfur resources, low production costs, and environmental friendliness, have a high theoretical specific capacity(1675 mAh·g-1). However, polysulfide shuttle causes serious problems such as the passivation of metal lithium anode, the decrease of battery capacity and coulomb efficiency, and hinders its practical applications. It is considered to be an extremely effective strategy to introduce a barrier layer to restrain polysulfide shuttle between the cathode and anode, which presents excellent performance in alleviating polysulfide shuttle, improving the utilization efficiency of active materials and extending cycle life and cycle stability. Herein, the research progress of the functional lithium sulfur battery separators is reviewed. Furthermore, the future research trend is also predicted.
Contents
1 Introduction
2 The principle and configuration of lithium-sulfur batteries
3 Technical challenges of research and application
4 Research development of functional separator
4.1 Functional separator with adsorption
4.2 Functional separator with catalytic function
4.3 Functional separator with electrostatic repulsion
4.4 Functional separator with physical barrier
4.5 Novel multifunctional separator fabrication
4.6 Functional separator for protecting Li metal anode, synergistically
5 Conclusion and outlook
Concentrated Electrolyte for Lithium/Li-Ion Batteries
Zenghua Chang, Jiantao Wang, Zhaohui Wu, Jinling Zhao, Shigang Lu
2018, 30 (12): 1960-1974 | DOI: 10.7536/PC180344
Published: 15 December 2018
Abstract
The conventional non-aqueous electrolyte based on 1 mol·dm-3 LiPF6/EC has been used for two decades in Li-ion batteries. With the rapid development of higher energy and power densities Li-ion batteries and Lithium batteries (such as Li-O2, Li-S,etc.), the electrolyte, as an indispensable component in rechargeable batteries, comes to the stage of innovation. Considerable efforts have been made on the research of several new types of electrolytes such as ionic liquid, polymer electrolytes and inorganic solid electrolytes. However, their commercial applications are hampered due to their intrinsic problems. Therefore, researchers begin to revisit the non-aqueous solution, and pay more attention on the concentrated electrolyte. This review summarizes the research on concentrated electrolytes including the development history, the solution structure, the classification criteria, the physicochemical property and the compatibility with electrode, the specific transport properties of lithium ions in the bulk solutions and the interface of electrolyte/electrode, as well as the compatibility of electrolyte and electrode. Besides, the main problems of concentrated electrolyte such as high viscosity and low ionic conductivity are briefly summarized, and the corresponding improvement measures are proposed. Finally, we highlight the research direction of concentrated electrolyte in the future, and provide an idea for the design of new type electrolyte.
Contents
1 Introduction
2 The development of concentrated electrolyte
3 Structural characteristics of concentrated electrolyte
3.1 The effect of lithium salt concentration on the structure of concentrated electrolyte
3.2 The effect of solvent on the structure of concentrated electrolyte
3.3 The effect of anions on the structure of concentrated electrolyte
4 The classification of concentrated electrolyte
5 Physical chemistry and interface properties of concentrated electrolyte
5.1 Thermal stability
5.2 Electrochemical stability
5.3 Ionic transfer property
5.4 Compatibility with electrode materials
6 The disadvantage of concentrated electrolyte
7 Conclusion
Investigation of the Mechanism of Cellular Uptake, Distribution and Toxicity of the DNA ‘Light-Switch’ Ru(Ⅱ) Polypyridyl Complexes
Benzhan Zhu, Xuan Xiao, Xijuan Chao, Miao Tang, Rong Huang, Jie Shao
2018, 30 (12): 1975-1991 | DOI: 10.7536/PC180421
Published: 15 December 2018
Abstract
Since the discovery of DNA as the genetic material carrier, the work towards the elucidation of DNA structure within the cell nucleus has become of great importance. Fluorescent microscopy using luminescent and cell membrane permeable organic DNA-binding molecule as probes is a well-established technique towards achieving this goal. Barton's group discovered that the cationic ruthenium complex[Ru(bpy)2(dppz)]2+ (bpy=2,2'-bipyridine, dppz=dipyrido[3,2-a:2',3'-c] phenazine) functions as a molecular ‘light switch’ for DNA. Since then, there has been great attention drawn to the DNA binding properties of polypyridyl complexes of d6 octahedral metal ions, specifically towards the development of highly sensitive and structure-specific DNA probes.Until recently the research has been largely focused on the development of in vitro probes. However, few studies involving direct imaging of DNA in live cells with such systems have had very limited success, with poor membrane permeability still being ascribed as the major limiting factor. We found that not only the cellular, but more interestingly and importantly, the nuclear uptake of[Ru(bpy)2(dppz)]2+ is remarkably enhanced by pentachlorophenol and two other structurally unrelated biochemical agents. Furthermore, enantioselective imaging of live-cell nuclear DNA is observed between the two chiral forms of Ru(Ⅱ) complexes. The underlying molecular mechanism is found to be the formation of novel lipophilic and relatively stable ion-pair complexes. This represents the first report for an unprecedented new method for delivering the DNA ‘light-switching’ Ru(Ⅱ) complexes into the nucleus of living cells via ion-pairing, which could serve as a promising general live-cell delivering method for other potentially bio-medically but cell-impermeable metal complexes.
Contents
1 Introduction
2 Predominant interactions between metal chelates and DNA
2.1 Irreversible binding with DNA
2.2 Reversible binding with DNA
3 Binding with intracellular DNA
3.1 Cellular uptake mechanism
3.2 Potential luminescent probe for intracellular DNA
3.3 Hydrophobicity and cellular uptake regulation
3.4 Appending targeting group for cellular uptake promotion
3.5 Active transport of chelates
3.6 Enhanced cellular uptake of “DNA light switch” Ru(Ⅱ) complex via forming lipophilic ion-pairing complexes
4 Methods for assessing cellular uptake
4.1 Transmission electron microscope
4.2 Raman spectra
4.3 Molecular labeling methods with fluorophore
4.4 Methods for quantitative uptake measurements
5 Cytotoxicity
6 The medical value for Ru(Ⅱ) polypyridyl complexes
The Structure of Hexaaluminate and Application in High-Temperature Reaction
Yanyan Zhu, Zongyang Yue, Wen Bian, Ruilin Liu, Xiaoxun Ma, Xiaodong Wang
2018, 30 (12): 1992-2002 | DOI: 10.7536/PC180406
Published: 15 December 2018
Abstract
Hexaaluminate materials exhibit remarkable thermal stability due to their peculiar layered structure. The Al3+ ions in the hexaaluminate lattice can be substituted by transition or noble metals, giving rise to redox centers for a variety of reactions. Oxygen in the mirror plane of hexaaluminate is loosely packed, making it a preferential diffusion route of oxygen. All of these favor the application of hexaaluminate in high-temperature oxygen-involved reaction. In this review, the structure of hexaaluminate is firstly introduced. Furthermore, the effect of structure type(magnetoplumbite and β-Al2O3) and metal substitution on the microstructure of hexaaluminate (especially metal chemical state) are carefully described. Then we discuss recent advances of hexaaluminate in high-temperature oxygen-involved reactions, such as, catalytic combustion of CH4, process-gas N2O abatement, decomposition of N2O as a propellant, CH4 chemical looping combustion and reforming, with a special emphasis on the relationship between the microstucture and reaction performance. At last, a brief summary and an outlook are given.
Contents
1 Introduction
2 Crystal structure of hexaaluminate
2.1 Structural type and metal substitution
2.2 Anisotropic crystal growth and preferential diffusion of oxygen
3 Effect of metal substitution on microstructure of hexaaluminate
3.1 Substitution of large cations in the mirror plane
3.2 Substitution of Al3+ ions by transition metal ions
3.3 Substitution of Al3+ ions by noble metal ions
4 High temperature application of hexaaluminate
4.1 Catalytic combustion of methane
4.2 Catalytic decomposition of nitrous oxide
4.3 Chemical looping combustion and reforming of methane
5 Conclusion and outlook
The Application of Biomimetic Superoleophobic Materials under Harsh Operating Conditions
Jianwen Shao, Fuchao Yang, Zhiguang Guo
2018, 30 (12): 2003-2011 | DOI: 10.7536/PC180135
Published: 15 December 2018
Abstract
The superamphiphobicity includes extremely nonwetting phenomena of superhydrophobicity and superoleophobicity. Superoleophobicity is relatively harder to realize but has a lot of promising applications. The biomimetic methods are usually adopted to acquire superoleophobic materials, including building up rough structures and modifying materials with low surface energy on surfaces. The rough structures are easy to be destroyed by mechanical effects such as friction and impact, since many situations of using superoleophobic materials involve the gear friction and bearing transmission. The low surface energy materials tend to decompose under UV irradiation, however, a range of solar devices which include solar panels have to work outdoor. Superoleophobicity with UV resistance applied on these devices helps to prolong service life while maintaining the working effiency, which can save energy and fulfill eco-friendly industry. For solving these problems, researchers study reliability of superoleophobic materials under different kinds of harsh circumstances. This review summarizes the latest advances on the reliable performances of superoleophobic material under ultraviolet irradiation; repeated impact, high temperature, and other complicated conditions. Because most of industrial environments accompanied with corrosion and friction, this review sets an emphasis on superoleophobic materials' anticorrosion and friction resistance properties. In the end, we summarize the drawbacks and advantages of plentiful experiments, the problems of products, the promising breakthrough, and the standpoints about how to improve superoleophobic materials' performance and stability under the harsh operating conditions.
Contents
1 Introduction
2 The effect of harsh environment on superoleophobic performance
2.1 The performance of superoleophobic material under acid-base corrosion conditions
2.2 The performance of superoleophobic material under water environment
2.3 The stability of superoleophobic material under ultraviolet
2.4 Researches and developments of superoleophobic phenomena at extreme temperatures
3 Effect of mechanical and force on the stability of superoleophobicity
3.1 The influence of friction condition on the properties of superoleophobicity
3.2 The effect of load on superoleophobicity capacity
3.3 The durability of superoleophobic coatings under mechanical impact
4 Conclusion and outlook
Application of the Tianium, Nickel and Iron Complexes in the Hydrosilylation
Xiaoling Yang, Ying Bai*, Jiayun Li, Zinan Dai, Jiajian Peng*
2018, 30 (12): 2012-2024 | DOI: 10.7536/PC180446
Published: 15 December 2018
Abstract
Tianium, nickel and iron complexes as catalysts have been widely applied in numerous catalytic organic reactions, in which these complexes show excellent catalytic performance and have been recognized as very important research field. We summarize the recent progress in the synthesis of titanium, nickel and iron complexes and their application in the catalytic hydrosilylation of alkenes, alkynes, carbonyl compounds and other unsaturated double bond, triple bond compounds. Furthermore, the deficiencies of the catalysts have been discussed. At last, the future development and prospects of these complexes as catalysts are also proposed.
Contents
1 Introduction
2 Application of the tianium complexes in the hydrosilylation
3 Application of the nickel complexes in the hydrosilylation
4 Application of the iron complexes in the hydrosilylation
5 Conclusion